Journal of Industrial and Engineering Chemistry 63 (2018) 1–11

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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Theoretical and experimental investigation on the removal of oil spill

by selective sorbents
Pavithra Narayanan, Abhaiguru Ravirajan, Avinash Umasankaran, D. Gnana Prakash* ,
P. Senthil Kumar*
Department of Chemical Engineering, SSN College of Engineering, Chennai 603 110, India

A R T I C L E I N F O A B S T R A C T

Article history:
Received 15 December 2017 In this research, oil sorption capacity of natural Peat moss and polymeric sorbents have been studied for
Received in revised form 11 January 2018 the removal of oil spills from aquatic media. A maximum absorption capacity of 22 times its self-weight
Accepted 23 January 2018 was observed for Nature sorb, in crude oil. The particle size equivalent of 100 mesh was found to have the
Available online 14 February 2018 maximum sorption capacity. Envirobond 403 provided the best oil retention capacity, with a minimum
weight loss of 2.4 g/7 g of oil. Water contact angle for Nature sorb and Sphag sorb were found to be
Keywords: 104.33
and 73.29
, respectively. FTIR confirms physical encapsulation as the principle of absorption.
Sorption capacity © 2018 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Kinetics
reserved.
Nature sorb
Sphag sorb
Envirobond 403

Introduction as in the process of oil production, distribution, and utilization,

Water, is of utmost importance in our day-to-day lives and the
motivation to preserve it is the need of the hour [1–3]. According to
United Nations World Water Development Report, about 2 million
tonnes of waste are discharged in the water bodies per day [4].
Also, recent studies show that around 1.5 million children die per
year due to the poor quality of water [5]. It is seen that the flora and
fauna dependent on the marine ecosystem also gets affected
polluting the food web causing eutrophication [6,7]. The major
causes for water pollution are domestic, industrial and agricultural
activities and other global changes [8–10]. Also, population growth
is one of the major factors as it led to industrial development and
this in turn has prompted environmental pollution [11]. In the past
few decades, numerous conventional methods have been proposed
to resolve the contaminants present in the aquatic ecosystem [12].
As the international standards for environment protection has
become more stringent, newer technologies have been developed
for enhanced separation and purification [7,13,14].
Crude oil and its distillation products have a major impact on
the living standards of human beings. However, the seas and
coastlines are polluted as a result of anthropogenic activities, such
* Corresponding authors.
E-mail addresses: gnanaprakashd@ssn.edu.in (D. G. Prakash),
senthilkumarp@ssn.edu.in (P. S. Kumar).
including discharges during normal operations of tankers [15].
Petrochemical industries and textile are significant contributors
too, contaminating the marine environment with production
discharges [9,16–24]. Discharge from industrial washers is
estimated to have 300–7000 mg/l of emulsified oil concentration
and about 30,000 mg/l of free floating oil [25,26]. These discharges
pose a risk of fire due to in situ combustion of oil and increase in
volatile organic compounds (VOC), leading to photochemical smog
[27,28]. Also, frequent oil-spill accidents during the oil exploration
and transportation processes have been reported so far [29–31].
The numbers are prone to increase, with enormous pressure on
drilling firms and oil companies, to make petroleum products
easily available in the global market. These marine oil spills have a
great impact on the environment and pose a major threat to the
aquatic ecosystem and birds [15,32].
On the economic front too, oil spills have an adverse effect,
including the loss of non-renewable energy resources and cost of
production and refining. The public and industries obtain a wide
range of benefits from the coastal and marine ecosystem [33–35],
that are in general categorized as ecosystem services; These
include supporting services, products such as fish and other food
resources and cultural services such as tourism, aesthetic pleasure,
etc. Hence, even a slightest disturbance in the marine ecosystem
has the potential for a multi-fold impact. Such impacts of oil spill
establish the pressing need for an effective clean-up method.

https://doi.org/10.1016/j.jiec.2018.01.031
1226-086X/© 2018 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
2 P. Narayanan et al. / Journal of Industrial and Engineering Chemistry 63 (2018) 1–11

Though many techniques for oil spill clean-up have been explored
[36–38], each method is faced with a variety of shortcomings.
In situ burning is the immediate response to an oil spill in
relatively small water bodies. In this technique, the thick oil slick is
burnt on the surface of water, to prevent the marine ecosystem
from being affected. It requires specialized fire-resistant booms
and igniters [39]. Though it is a simple, quick technique capable of
removing oil at very high rates, it has limitations in the form of
viscous residues that can sink and affect the sea bed, release of
potential irritants [40] and possibility of secondary fires [37]. The
basic and most commonly used method of oil spill clean-up is
physical separation by the use of skimmers and booms [36].
Skimmers are extensively used to separate floating oil from surface
of water, while booms are used to contain the spill in a narrow
region. The efficiency of skimmer however, depends on weather
conditions. The U.S. Environmental Protection Agency (1999)
“Understanding oil spill and oil spill response” stated that
skimmers tend to recover more water than oil in rough or choppy
waters. Other limitations include the process being labour and
equipment intensive [36], attrition of booms under harsh sea
conditions, and higher operating cost resulting from poor
efficiency [41]. Another evolving method for marine oil spill
clean-up is bioremediation, which involves addition of “oil-eating”
microorganisms to degrade complex chemical compounds to
simple molecules [42]. Though many authors consider it as a cost
effective and environment friendly method for treating oil spill in
comparison to other techniques [43–47], others have pointed out
Table 1
Properties of peat moss.
Physical state Solid
Moisture content (kg of water/kg of sorbent) 0.1
Colour Brown
Appearance Fibrous particles
Specific gravity (water = 1) 0.90
pH 4.6
Auto ignition temperature 260
C
that bioremediation is not very effective in degradation of heavy
components and polycyclic aromatic hydrocarbons (PAHs), asso-
ciated with crude oil [37,48–52]. Also, this technique is limited by
various abiotic factors such as fixed nitrogen content, temperature
and oxygen availability [37]. Atlas and co-workers suggested the
addition of fertilizers to improve fixed nitrogen concentration and
thereby enhance degradation efficiency [48]. However, this
increased nutrient concentration will lead to eutrophication,
resulting in depleted oxygen content, indirectly affecting the
degradation efficiency [46]. In addition, this technique is highly
compound specific, and there is a possibility of the resultant
compound being more toxic than the original compound [42]. In
certain cases, dispersants or surfactants are used to reduce the
interfacial tension between oil and water, and thereby aid in
natural degradation of hydrocarbons in crude oil. These disper-
sants are proven to have maximum efficiency when used
immediately after the occurrence of oil spill, before the lighter
hydrocarbons escape [53]. But, these dispersants may result in
finer droplets that are harmful to aquatic life [54].
One of the most effective methods to combat oil spills is by
using oleophilic, hydrophobic sorbents. These sorbents absorb oil
more than the self-weight and transform it to solid or semi-solid
state for easy disposal or re-use. This is an attractive method owing
to the possibility of complete removal and reuse of oil. Literature
review shows that a variety of sorbents have been previously
explored, and these sorbents can be broadly categorized into
inorganic mineral sorbents, synthetic organic sorbents, natural
organic sorbents mainly from agricultural sources, and the very
promising magnetic nanocomposites [55–85], Pham and company
have reported the synthesis of cost effective super-hydrophobic
sponges by silanization of commercially available melamine
sponges, through a process of solution-immersion [55]. It had a
water contact angle of 151.0
and a capacity to absorb 82–163 times
its own weight of oil and other organic solvents, depending on the
polarity and density of the oil. Several others have worked on
similar inorganic sorbents. But these sorbents are found to have
numerous shortcomings; they may cause contamination of sea
bed, and leakage of oil, owing to low retention capacity [55]. Also,

Table 2
Properties of Envirobond 403. Table 3
Density of the oils measured using gravimetric method.
Physical state Solid
Medium Density of media in kg/m3 at 15
C
Moisture content (kg of water/kg of sorbent) 0.0
Colour White Crude oil 887
Appearance Powder form Engine oil 882
Specific gravity (water = 1) 0.91 Lube oil 880
pH 8.31 Diesel 820
Auto ignition temperature 352
C Petrol 710

Fig. 1. Oils used for absorption and kinetic studies; A – petrol, B – diesel, C – lube oil, D – engine oil with Sudan IV dye for differentiation and E – crude oil. (Oil samples were
stored at 4
C and brought to room temperature before performing experiments).
 P. Narayanan et al. / Journal of Industrial and Engineering Chemistry 63 (2018) 1–11 3

Fig. 2. Diagrammatic representation of absorption and kinetic studies; A – 200 mg of Peat moss in nylon bag of pore size 120 mm, before absorption. B – Peat moss in nylon
bag, during absorption in 50 ml of petrol. C – Peat moss + petrol after absorption.

Fig. 3. Sorbents before and after absorption of petrol. A – Peat moss, B – Peat moss with petrol, C – Sphag sorb, D – Sphag sorb with petrol, E – Envirobond 403, F – Envirobond
403 with petrol.

they are difficult to handle on site owing to their granular form
[86]. A certain study on the preparation of sorbent consisting of
polyvinyl chloride (PVC)/polystyrene (PS) fibre, by the process of
electrospinning shows that the sorption capacity was determined
to be in the range of 38–119 g/g [76]. However, a major limitation of
synthetic organic sorbents in general, is their non-biodegradability
[37], which can be countered only by improving their reusability.
Organic vegetable products and agricultural wastes such as corn
cob, wood fibre, cotton fibre, cellulosic kapok fibre, peat, rice husk,
bagasse, etc. have a good oil sorption capacity [27,64,71,79,74,87]
and have been studied extensively, even with surface modification.
The oil sorption capacity of kapok fibre was examined in three
different oils – diesel, hydraulic oil and engine oil, and found
maximum sorption of 45 g/g in hydraulic oil [86]. In general, the
efficiency of oil removal depends upon the sorbent used.
Though natural sorbents are eco-friendly, and aid in proper
utilization of waste, their sorption capacity is lesser than some of
the synthetic sorbents. Each sorbent has its own advantages and
limitations in terms of sorption capacity, retention, oil–water
selectivity, and their properties also depend on the type of oil to be
sorbed. It is essential to take all these factors into consideration
while choosing a sorbent for a particular application. Though a few
published works have studied the kinetics of oil sorption and
sorption capacity [88], a comparative study using commonly used
oil media, which has not been worked on so far, will provide a
wider perspective in the choice of sorbent. Hence this work aims to
4 P. Narayanan et al. / Journal of Industrial and Engineering Chemistry 63 (2018) 1–11
compare the absorption capacity and study the kinetics involved in
sorption of five different oils (Crude, petrol, diesel, lube, and engine
oil) by two natural sorbents – Nature sorb (Peat moss), Sphag sorb
and a synthetic sorbent – Envirobond 403. The natural sorbents are
derived from modification of Sphagnum Peat moss, a sorbent that
has been used for decades for the removal of organic compounds
and heavy metals, owing to its low cost and zero toxicity.
Envirobond 403 on the other hand, is a relatively new sorbent
that works on the principle of solidification, enabling its use as
solid fuel, and in the production of asphalt, roofing material and
other tar-like compounds.
Materials
Nature sorb (Peat moss) and Sphag sorb
The two natural sorbents – Peat moss and Sphag sorb were
supplied by Equinox Global Trading, UAE. Nature sorb is a treated
or activated form of Sphagnum Peat moss. Sphagnum initially had
a water holding capacity of 4–6.35 kg/kg. The moisture content was
brought down from 90% to 60% by bog preparation and aeration. It
was further heat treated and air dried to bring its moisture content
to 10%. Thus, the peat was converted into a hydrophobic and
oleophilic sorbent. The individual fibre had the ability to be
suspended in the air. When the fibres were placed on the surface of
water, it floated on the surface, causing slight water surface
depression due to the inability of water to wet the Peat moss fibres,
Fig. 4. Comparison of percentage of absorption of petrol, diesel, lube oil, engine oil and crude oil on Sphag sorb, as a function of time. (Mass of Sphag sorb = 2 mg, volume of oils
used = 50 ml, temperature of absorption medium = 32
C).
which is possible due to a high interfacial surface tension. This
property is crucial due to the possibility of sorbent encountering
water before oil in sorption application. Properties of Peat moss as
obtained from manufacturer's MSDS are presented in Table 1.
Sphag sorb shares its origin with nature sorb (Sphagnum Peat
moss). However, varies in heat treatment, such that its moisture
content (14%) is slightly higher than that of nature sorb.
Envirobond 403
The synthetic sorbent, Envirobond 403, was obtained from
Steve Spangler Science. It is a hydrophobic, oleophilic block
copolymer, that encapsulates the oil film to form a rubber like
solid, that floats on the surface of water for easy removal.
Properties of Envirobond 403 are tabulated in Table 2.
Oils
Petrol, diesel, lube oil and engine oil used were of commercial
grade, purchased from Shell Petroleum Limited, Chennai, Tamil
Nadu, India. The crude samples were collected from Chennai
Petroleum Corporation Limited (CPCL). All the samples were stored
at 4
C to maintain their respective characteristics. The oil samples
are shown in Fig. 1 (A – petrol, B – diesel, C – lube oil, D – engine oil
with Sudan IV dye for differentiation and E – crude oil). Density of
the oils used are measured using gravimetric method, and the
values are tabulated in Table 3.
 P. Narayanan et al. / Journal of Industrial and Engineering Chemistry 63 (2018) 1–11
Methodology
Absorption and kinetic studies
The batch absorption and kinetic studies were conducted at
ambient temperature (32
C). A diffusion bag of dimension
3 cm  3 cm was fabricated from nylon mesh of pore size
120 mm. The measurement of swelling capacity of sorbents were
carried out in the different medium – petrol, diesel, engine oil, lube
oil and crude, without water. Approximately 200 mg of the sorbent
were fed into the diffusion bags. The weight of the nylon bags was
weighed before and after feeding the sorbent sample in it. Each
nylon bag was placed in the medium containing 50 ml of oil, such
that the sorbent within the bag was completely immersed. The
bags were taken out after various time intervals (1, 5, 10, 20, 30, 60,
300, 900, 1800, and 3600 s). The lower ends of the bags were gently
wiped with tissue to remove excess oil and the final weight of the
bags were tabulated (Fig. 2).
The gravimetric swelling capacity was calculated using the
following formula:
Wt  W
Swelling capacity ¼  100%
W
where Wt is the weight of the swollen sample at time t and W is the
weight of the dry sample. The above procedure was repeated for all
the oil–sorbent combinations. Also, three replications were
obtained for all data points. Fig. 3 shows images of the three
sorbents before and after absorption of petrol.
Fig. 5. Comparison of percentage of absorption of petrol, diesel, lube oil, engine oil and crude oil on Peat moss, as a function of time. (Mass of Peat moss = 2 mg, volume of oils
used = 50 ml, temperature of absorption medium = 32
C).
5
Characterization
Scanning electron microscopy (SEM)
Porosity of the sorbent is an important parameter of its oil
sorption capacity. Morphology of the three sorbents before and
after absorption was analysed by scanning electron microscopy
(SEM, Carl Zeiss EVO 18). The samples were mounted on round
stainless-steel sample holders with doublesided conductive
adhesive tapes. SEM images were examined using accelerating
voltage at 5 kV. Around 0.5 g of sorbent was placed inside the
sample cell for surface analysis.
Contact angle measurement
Water contact angle of the three sorbents was measured to
validate their hydrophobicity. The sorbents (Peat moss, Envirobond
403 and Sphag sorb) were pelletized using Cold pressing
equipment. Contact angle measurements were performed on
the surface of pelletized sorbents using Digidrop GBX contact angle
goniometer. De-ionized water of volume 1 ml was placed on the
sample using a dropper and the image was recorded using
ð1Þ DROPimage Advanced software in a desktop connected to the
instrument. The contact angles were evaluated by determining the
shape of the drop and calculating the slope of the tangent at the
liquid-solid interface line on both sides of the droplet. The contact
angle measurements were performed thrice for each sorbent
sample and they were averaged.
6 P. Narayanan et al. / Journal of Industrial and Engineering Chemistry 63 (2018) 1–11

Fourier transform infrared spectroscopy (FTIR)
Infrared spectroscopy is a very useful tool for obtaining rapid
information about the molecular structure of sorbents and
chemical changes if any, taking place due to the absorption of
oil [89]. FTIR spectra of the three sorbents before and after
absorption of crude oil were run on KBr pellets (1 wt%). Pellets
were stored in a desiccator to prevent moisture/water which might
induce spectral perturbations at 3400 and 1630 cm1 [90].
available in Table 1. The oil with high density can easily adhere to
the sorbent and be kept in the assembly [75]. Also, these sorbents
with higher density have higher viscosity, that prevent the oil from
draining out as easily from the pores of the sorbent assembly and
hence higher absorption capacity was observed. Similar

Results and discussion

Absorption study

The amount of oil retained in the sample bag, after lifting it from
the oil bath was analysed. For determination of oil sorption
capacity, the oil amount retained in the sorbent assembly after 24 h
of sorption (so that the system is in steady state), was measured.
Figs. 4–6 represent the oil absorption capacity of Sphag sorb, Peat
moss, and Envirobond 403 respectively in the five different oil
media. It is evident that absorption capacity was maximum for
Peat moss, absorbing nearly 22 times its initial weight for crude oil,
followed by Sphag sorb (19 times), with Polymer being the least
absorptive (12 times). Comparing the media, it is clear that
absorption is favourable in the following order: crude > engine
oil > lube oil > diesel > petrol. Fig. 7. Effect of particle size (in mesh number) on crude oil absorption capacity of
This preference of absorption is due to the difference in density the three sorbents. (Mass of sorbents = 2 mg, volume of crude oil used = 50 ml,
of the media, that follows the same order. The density data is temperature = 32
C).

Fig. 6. Comparison of percentage of absorption of petrol, diesel, lube oil, engine oil and crude oil on Envirobond 403, as a function of time. (Mass of Envirobond 403 = 2 mg,
volume of oils used = 50 ml, temperature of absorption medium = 32
C).
 P. Narayanan et al. / Journal of Industrial and Engineering Chemistry 63 (2018) 1–11 7

Table 4
Kinetic results for the removal oil spills by sorbents.

Sorbent Oil k2 R2
Peat moss Petrol 0.00074301 0.98267
Diesel 0.001752979 0.99734
Engine oil 0.002340276 0.99952
Lube oil 0.002140804 0.9998
Crude oil 0.002522712 0.99986
Envirobond 403 Petrol 0.001301582 0.97077
Diesel 0.001821178 0.98744
Engine oil 0.001228348 0.99575
Lube oil 0.001187743 0.99906
Crude oil 0.001482112 0.99843
Sphag sorb Petrol 0.000821113 0.98728
Diesel 0.00147396 0.9792
Engine oil 0.000191406 0.97445
Lube oil 0.000147348 0.99163
Crude oil 0.00045869 0.99827

Fig. 8. Kinetic plot for Peat moss.

Effect of particle size

Particle size is one of the factors affecting absorption

percentage. The three sorbents under consideration were analysed
for absorption capacity as a function of particle size. This was
carried out by performing absorption study discussed in
Section “Absorption and kinetic studies” for a period of 1 h with
crude oil as the medium at room temperature (32
C), after size
separation by agitating in a RoTap sieve shaker machine for 30 min.
The various sieves used were 32, 48, 64, 100 and PAN. The results
obtained are presented in Fig. 7. The Sieve size is represented as
Tyler mesh number. From Fig. 7, it is found that the particle size has
a significant effect on absorption percentage. As expected, the
particle size decreases, the absorption percentage increases and
the maximum absorption was observed for particles retained in
100 mesh sieves. Smaller the particle size, greater is the surface
area to volume ratio. As a result, the distance to be covered by the
oil molecule from the surface of the sorbent to the inside is lesser,
and hence better absorption capacity is achieved. Although, fine
powder has better oil sorption efficiency, its handling and
Fig. 9. Kinetic plot for Sphag sorb.
production costs need to be evaluated before commercial
application.

Batch kinetic study

For application of sorbent in real time oil spill, the kinetics of

Fig. 10. Kinetic plot for Envirobond 403.
observations have been reported for other oil absorption materials
[60,91,92]. The absorption capacity of Peat moss was also found to
be higher than that of other sorbents, as reported in the literature
[87,93].
sorption needs to be understood. Hence oil absorption is studied as
a function of time for the three sorbents. The sorbents under
consideration were analysed in the same procedure as in
Section “Absorption and kinetic studies”. All the experimental
results obtained were examined and in order to obtain a better
understanding of the absorption process, the experimental data
was further analysed using the available kinetic models. The
pseudo-first order model is given as follows:
dQ t
¼ k1 ðQ max  Q t Þ ð2Þ
dt
where Qt is the sorption capacity of the sorbent at time t, Qmax is
the sorption capacity of the sorbent at equilibrium, k1 is the rate
constant for pseudo-first order kinetics.
Integrating (2) with the limit Qt = 0 at t = 0, we get,
 
Q max
ln ¼ k1 t ð3Þ
Q max  Q t
The absorption process is said to follow the first order kinetics if
the plot between ln½Q max =ðQ max  Q t Þ versus time (t) gives a
straight line passing through the origin.
8 P. Narayanan et al. / Journal of Industrial and Engineering Chemistry 63 (2018) 1–11

Table 5
Comparison of sorption capacity of commonly used sorbents with those under study.

S. no. Sorbent Absorption capacity (grams of oil/gram of sorbent) References

1 Nature sorb (Peat moss) 11.8 Present study
2 Envirobond 403 22 Present study
3 Sphag sorb 19.6 Present study
4 Carbonised fir fibre 10 [65]
5 Expanded perilite 3.4 [57]
6 Nonwoven polypropylene 10 [81]
7 Butyl rubber 15 [81]

Fig. 11. Loss in weight of sorbents–petrol mixture as a function of time (in days).
Fig. 13. Static water contact angle results on Sphag sorb as a function of time. Inset:
A representative optical photograph of a water droplet on Sphag sorb.

Fig. 14. A representative optical photograph of Envirobond 403 granules adhering

Fig. 12. Static water contact angle results on Peat moss as a function of time. Inset: A
representative optical photograph of a water droplet on Peat moss.
Similarly, the pseudo-second order kinetic model is depicted as,
dQ t
¼ k2 ðQ max  Q t Þ2 ð4Þ
dt
Integrating (4) we get,
t 1 1
¼ þ t ð5Þ
Q t k2 ðQ max Þ2 Q max
The absorption process is said to follow pseudo-second order
kinetics if the plot between t/Qt versus time (t) generates a straight
line passing through all the data points. The experimental data
obtained were analysed and the plot between t/Qt versus time (t) is
a straight line and passes almost all the data points (Figs. 8–10)
with a correlation coefficient (R2) value of >0.97 (Table 4) as
to the dropper.
compared with the pseudo-first order kinetic model (figure not
shown). This indicates that the absorption process followed the
pseudo-second order kinetics (Table 5).
Retention capacity
Retention is the ability of the sorbent to hold the medium
without any leakage. It plays a significant role in the transport of
absorbed material from the affected site. Though water sorption is
negligible and clearly lower than the oil sorption, it depends on the
amount of sorbent used. Works in literature have showed that an
excess of sorbent can cause the retention of water on the sites not
impregnated by oil [94]. To avoid this problem, the oil retention
capacity must be taken into consideration and only the necessary
amount of sorbent must be used and dispersed on the water
 P. Narayanan et al. / Journal of Industrial and Engineering Chemistry 63 (2018) 1–11 9

surface. Therefore, the retaining capacity of the three sorbents
under consideration were compared. Since petrol had the
maximum volatility among the five media, it was used to study
the retention. Seven grams of petrol were added to the sorbent
samples such that the samples were completely saturated. Mass of
the sorbent in the nylon pockets was measured every day, over a
period of 7 days. A plot between weight loss (grams, in comparison
to the initial weight) and time (days) shows the retention capacity
of every sorbent. Fig. 11 shows that the loss in weight due to the
escape of petrol was very high initially, but slows down gradually
in the first three days, before attaining a constant weight in a
maximum of four days. Weight loss is maximum in the case of
Sphag sorb (6.3 g), closely followed by Peat moss (5.6 g), whereas it
is minimum in the case of polymer (2.4 g). The loss in weight is due
to high volatility of petrol. The physical and chemical
characteristics of the sorbents such as the physical configuration
including surface roughness, porosity, and fineness, as well as
molecular arrangement could affect the retention capacity of
sorbent. Envirobond 403 works on the principle of solidification,
forming a rubbery mass by encapsulating the oil between the
cross-linking structure, which is a common feature in solidifiers
[81]. This could be a contributing factor to the high retention found
in the case of Envirobond 403.
Contact angle
Hydrophobicity of the sorbents was characterized by their
water contact angle measurements. As shown in Fig. 12, the water
contact angle of Peat moss increased with time, from 0
to 104.33

after 5 s of addition of water, confirming its hydrophobic nature,

Fig. 15. FT-IR spectrum of the sorbents before and after absorption of crude oil.
10 P. Narayanan et al. / Journal of Industrial and Engineering Chemistry 63 (2018) 1–11
Fig. 16. SEM images of the sorbents before absorption (A – Peat moss, B – Sphag sorb, C – Envirobond 403) and after absorption (D – Peat moss, E – Sphag sorb, F – Envirobond
403).
which is an essential parameter for selectivity of oil over water, in
case of marine oil spills. In the case of Sphag sorb, the water contact
angle was found to be 73.29
(Fig. 13), showing that it is less
hydrophobic than Peat moss. This is in tune with the moisture
content data obtained from the manufacturer (Sphag sorb consists
of 14% moisture while Peat moss has only 10% moisture content).
The higher hydrophobicity of Peat moss also supports its better
absorption capacity in comparison to Sphag sorb. On the other
hand, contact angle could not be determined for Envirobond 403,
because the polymer particles were found to adhere to the dropper
(Fig. 14).
Fourier transform infrared spectrometry (FTIR)
The FTIR spectra of the three sorbents before and after
absorption of crude oil are presented in Fig. 15. It can be concluded
that there is no significant change in the spectral peaks of the three
sorbents before and after absorption of crude oil, except in the
wave number 2922  3 cm-1corresponding to CH alkane stretch-
ing, common for all the three sorbents, which can be attributed to
addition of crude oil. Therefore, this absorption is a result of
physical phenomena of encapsulation. In addition, polymer has a
significant peak at 698 cm1 corresponding to aromatic C H
bending vibrations, 1453 cm1 methyl group bending vibrations.
The broad peak close to 1600 cm1 and beyond 3330 cm1 in all the
samples correspond to the (OH) band (scissoring mode/H O H)
of water.
Scanning electron microscopy (SEM)
SEM analyses were carried out consecutively to compare the
morphology of three different sorbent materials. The surface
morphology of Peat moss, Sphag sorb and Envirobond 403 are
shown in Fig. 16A–C respectively. The surface structures of all three
sorbent materials were rough and irregular. A major pore structure
occurs with a series of irregular cavities distributed over the
surface of Peat moss, Sphag sorb and Envirobond 403. Compare to
Sphag sorb and Envirobond 403, Peat moss has a large number of
meso- and macropores on its surface. These mesopores are
responsible for the large surface area of Peat moss. The absorption
mostly takes place in these mesopores of Peat moss. Thus, it clearly
observed that the Peat moss has better morphology for oil spill
sorption.
Conclusion
The present investigation identified that the synthetic sorbent,
Envirobond 403 has1.86 times lesser absorption capacity than the
two natural sorbents. The natural sorbents offer eco-friendly
solution to oil spill clean-up, with Peat moss having the maximum
sorption capacity, of 22 times its self-weight among the three
sorbents. However, unlike the natural sorbents, Envirobond 403
being a polymer, does not contain cellulose and hence can be used
in oil spills, where the water contains cellulose degrading
microbes. Also, with high retention capacity that is 2.6 and 2.3
times that of Sphag sorb and Nature sorb respectively, it is useful in
applications where the absorbed oil needs to be transported to a
different location. Moreover, its high water-contact angle of
104.33
ensures its selectivity towards oil. Since absorption in
the three sorbents involve only physical interactions, it is possible
to recover the sorbed oil efficiently, which has scope for further
study.
References
[1] T.A. Saleh, V.K. Gupta, J. Colloid Interface Sci. 371 (1) (2012) 101–106, doi:
http://dx.doi.org/10.1016/j.jcis.2011.12.038.
[2] T.A. Saleh, V.K. Gupta, Environ. Sci. Pollut. Res. 19 (4) (2012) 1224–1228, doi:
http://dx.doi.org/10.1007/s11356-011-0670-6.
[3] R. Saravanan, N. Karthikeyan, V.K. Gupta, E. Thirumal, P. Thangadurai, V.
Narayanan, A. Stephen, Mater. Sci. Eng. C 33 (4) (2013) 2235–2244, doi:http://
dx.doi.org/10.1016/j.msec.2013.01.046.
[4] T.A. Saleh, V.K. Gupta, Adv. Colloid Interface Sci. 211 (2014) 93–101, doi:http://
dx.doi.org/10.1016/j.cis.2014.06.006.
[5] R. Saravanan, V.K. Gupta, V. Narayanan, A. Stephen, J. Taiwan Inst. Chem. Eng.
45 (4) (2014) 1910–1917, doi:http://dx.doi.org/10.1016/j.jtice.2013.12.021.
[6] A. Mittal, J. Mittal, A. Malviya, V.K. Gupta, J. Colloid Interface Sci. 340 (1) (2009)
16–26, doi:http://dx.doi.org/10.1016/j.jcis.2009.08.019.
[7] V.K. Gupta, R. Jain, A. Nayak, S. Agarwal, M. Shrivastava, Mater. Sci. Eng. C 31 (5)
(2011) 1062–1067, doi:http://dx.doi.org/10.1016/j.msec.2011.03.006.
[8] V.K. Gupta, I. Ali, T.A. Saleh, A. Nayak, S. Agarwal, RSC Adv. 2 (16) (2012) 6380,
doi:http://dx.doi.org/10.1039/c2ra20340e.
[9] R. Saravanan, E. Thirumal, V.K. Gupta, V. Narayanan, A. Stephen, J. Mol. Liq. 177
(2013) 394–401, doi:http://dx.doi.org/10.1016/j.molliq.2012.10.018.
[10] V.K. Gupta, T.A. Saleh, Environ. Sci. Pollut. Res. 20 (5) (2013) 2828–2843, doi:
http://dx.doi.org/10.1007/s11356-013-1524-1.
[11] R. Saravanan, S. Karthikeyan, V.K. Gupta, G. Sekaran, V. Narayanan, A. Stephen,
Mater. Sci. Eng. C 33 (1) (2013) 91–98, doi:http://dx.doi.org/10.1016/j.
msec.2012.08.011.
[12] R. Saravanan, S. Joicy, V.K. Gupta, V. Narayanan, A. Stephen, Mater. Sci. Eng. C 33
(8) (2013) 4725–4731, doi:http://dx.doi.org/10.1016/j.msec.2013.07.034.
[13] R. Saravanan, E. Sacari, F. Gracia, M.M. Khan, E. Mosquera, V.K. Gupta, J. Mol.
Liq. 221 (2016) 1029–1033, doi:http://dx.doi.org/10.1016/j.molliq.2016.06.074.
[14] T.A. Saleh, V.K. Gupta, Sep. Purif. Technol. 89 (2012) 245–251, doi:http://dx.doi.
org/10.1016/j.seppur.2012.01.039.
 P. Narayanan et al. / Journal of Industrial and Engineering Chemistry 63 (2018) 1–11
[15] J. Stone, M. Piscitelli, K. Demes, S. Chang, M. Quayle, D. Withers, Economic and
biophysical impacts of oil tanker spills relevant to vancouver, Can. Lit. Rev.
(2013) 1–153.
[16] G.M. Tehrani, S.B. Tavakoly Sany, R. Hashim, A. Salleh, Environ. Earth Sci. 75 (2)
(2016) 1–13, doi:http://dx.doi.org/10.1007/s12665-015-4918-1.
[17] V.K. Gupta, R. Jain, A. Mittal, T.A. Saleh, A. Nayak, S. Agarwal, S. Sikarwar, Mater.
Sci. Eng. C 32 (1) (2012) 12–17, doi:http://dx.doi.org/10.1016/j.
msec.2011.08.018.
[18] A. Mittal, J. Mittal, A. Malviya, D. Kaur, V.K. Gupta, J. Colloid Interface Sci. 342
(2) (2010) 518–527, doi:http://dx.doi.org/10.1016/j.jcis.2009.10.046.
[19] A. Mittal, D. Kaur, A. Malviya, J. Mittal, V.K. Gupta, J. Colloid Interface Sci. 337
(2) (2009) 345–354, doi:http://dx.doi.org/10.1016/j.jcis.2009.05.016.
[20] A. Mittal, J. Mittal, A. Malviya, V.K. Gupta, J. Colloid Interface Sci. 344 (2) (2010)
497–507, doi:http://dx.doi.org/10.1016/j.jcis.2010.01.007.
[21] V.K. Gupta, R. Kumar, A. Nayak, T.A. Saleh, M.A. Barakat, Adv. Colloid Interface
Sci. 193–194 (2013) 24–34, doi:http://dx.doi.org/10.1016/j.cis.2013.03.003.
[22] S. Rajendran, M.M. Khan, F. Gracia, J. Qin, V.K. Gupta, S. Arumainathan, Sci. Rep.
6 (1) (2016) 31641, doi:http://dx.doi.org/10.1038/srep31641.
[23] M. Ahmaruzzaman, V.K. Gupta, Ind. Eng. Chem. Res. 50 (24) (2011) 13589–
13613, doi:http://dx.doi.org/10.1021/ie201477c.
[24] N. Mohammadi, H. Khani, V.K. Gupta, E. Amereh, S. Agarwal, J. Colloid Interface
Sci. 362 (2) (2011) 457–462, doi:http://dx.doi.org/10.1016/j.jcis.2011.06.067.
[25] J.A. Fay, J. Hazard. Mater. 96 (June (2002)) (2003) 171–188.
[26] M.H. Weintraub, R.L. Gealer, A. Golovoy, M.A. Dzieciuch, H. Durham, Environ.
Prog. Sustainable Energy 2 (1983) 32–37.
[27] J.A. Fay, Combust. Sci. Technol. 7 (2007) 47–49.
[28] A.P. Altshuller, J.J. Bufalini, Environ. Sci. Technol. 5 (1971) 39–64.
[29] A. Loh, U.H. Yim, S.Y. Ha, J.G. An, M. Kim, Arch. Environ. Contam. Toxicol. 73 (1)
(2017) 103–117, doi:http://dx.doi.org/10.1007/s00244-017-0394-9.
[30] S. Castanedo, R. Medina, I.J. Losada, C. Vidal, F.J. Méndez, A. Osorio, J.A. Juanes,
A. Puente, J. Coast. Res. 226 (2006) 1474–1489, doi:http://dx.doi.org/10.2112/
04-0364.1.
[31] A.W. Maki, Environ. Sci. Technol. 25 (1) (1991) 24–29, doi:http://dx.doi.org/
10.1021/es00013a001.
[32] C.H. Peterson, S.D. Rice, J.W. Short, D. Esler, J.L. Bodkin, B.E. Ballachey, D.B.
Irons, Science 302 (2003) 2082–2086.
[33] B. Fisher, R.K. Turner, P. Morling, Ecol. Econ. 68 (3) (2009) 643–653, doi:http://
dx.doi.org/10.1016/j.ecolecon.2008.09.014.
[34] I. Ring, B. Hansjürgens, T. Elmqvist, H. Wittmer, P. Sukhdev, Curr. Opin. Environ.
Sustain. 2 (1–2) (2010) 15–26, doi:http://dx.doi.org/10.1016/j.
cosust.2010.03.005.
[35] S. Narvud, H. Lindhjem, K. Magnussen, Valuing Marine Ecosystem Services
Loss from Oil Spills for Use in Cost-Benefit Analysis of Preventive Measures
(2016), 124–137.
[36] V. Broje, A.A. Keller, J. Hazard. Mater. 148 (1–2) (2007) 136–143, doi:http://dx.
doi.org/10.1016/j.jhazmat.2007.02.017.
[37] A.A. Al-Majed, A.R. Adebayo, M.E. Hossain, J. Environ. Manag. 113 (2012) 213–
227, doi:http://dx.doi.org/10.1016/j.jenvman.2012.07.034.
[38] M. Divya, S. Aanand, A. Srinivasan, B. Ahilan, Int. J. Appl. Res. 1 (2015) 530–537.
[39] J.V. Mullin, M.A. Champ, Spill Sci. Technol. Bull. 8 (4) (2003) 323–330, doi:
http://dx.doi.org/10.1016/S1353-2561(03)00076-8.
[40] J. Schaum, M. Cohen, S. Perry, R. Artz, R. Draxler, J.B. Frithsen, D. Heist, M.
Lorber, L. Phillips, Environ. Sci. Technol. 44 (2010) 9383–9389.
[41] H.M. Brown, R.H. Goodman, C.F. An, J. Bittner, Spill Sci. Technol. Bull. 3 (4)
(1996) 217–220, doi:http://dx.doi.org/10.1016/S1353-2561(97)00016-9.
[42] V. Mary Kensa, J. Ind. Pollut. Control 27 (2) (2011) 161–168, doi:http://dx.doi.
org/10.1351/pac200173071163.
[43] P.V.O. Trindade, L.G. Sobral, A.C.L. Rizzo, S.G.F. Leite, A.U. Soriano, Chemosphere
58 (4) (2005) 515–522, doi:http://dx.doi.org/10.1016/j.chemo-
sphere.2004.09.021.
[44] A.I. Okoh, M.R. Trejo-Hernandez, J. Biotechnol. 5 (25) (2006) 2520–2525.
[45] M. Tyagi, M.M.R. da Fonseca, C.C.C.R. de Carvalho, Biodegradation 22 (2) (2011)
231–241, doi:http://dx.doi.org/10.1007/s10532-010-9394-4.
[46] B.M. Macaulay, D. Rees, Ann. Environ. Sci. 8 (March) (2014) 9–38.
[47] M. Cheng, G. Zeng, D. Huang, C. Lai, P. Xu, C. Zhang, Y. Liu, J. Wan, X. Gong, Y.
Zhu, J. Hazard. Mater. 312 (2016) 184–191, doi:http://dx.doi.org/10.1016/j.
jhazmat.2016.03.033.
[48] R.M. Atlas, Mar. Pollut. Bull. 31 (4–12) (1995) 178–182, doi:http://dx.doi.org/
10.1016/0025-326X(95)00113-2.
[49] R. Boopathy, Bioresour. Technol. 74 (1) (2000) 63–67, doi:http://dx.doi.org/
10.1016/S0960-8524(99)00144-3.
[50] Y. Liu, G. Zeng, H. Zhong, Z. Wang, Z. Liu, M. Cheng, G. Liu, X. Yang, S. Liu, J.
Hazard. Mater. 322 (2017) 394–401, doi:http://dx.doi.org/10.1016/j.jhaz-
mat.2016.10.025.
[51] M. Cheng, G. Zeng, D. Huang, C. Lai, P. Xu, C. Zhang, Y. Liu, Chem. Eng. J. 284
(2016) 582–598, doi:http://dx.doi.org/10.1016/j.cej.2015.09.001.
[52] M. Cheng, G. Zeng, D. Huang, C. Yang, C. Lai, C. Zhang, Y. Liu, Chem. Eng. J. 314
(2017) 98–113, doi:http://dx.doi.org/10.1016/j.cej.2016.12.135.
[53] R.R. Lessard, G. DeMarco, Spill Sci. Technol. Bull. 6 (1) (2000) 59–68, doi:http://
dx.doi.org/10.1016/S1353-2561(99)00061-4.
[54] R. Rico-Martínez, T.W. Snell, T.L. Shearer, Environ. Pollut. 173 (2013) 5–10, doi:
http://dx.doi.org/10.1016/j.envpol.2012.09.024.
[55] V.H. Pham, J.H. Dickerson, ACS Appl. Mater. Interfaces 6 (16) (2014) 14181–
14188, doi:http://dx.doi.org/10.1021/am503503m.
11
[56] S. Kizil, K. Karadag, G. Ozan Aydin, H. Bulbul Sonmez, J. Environ. Manag. 149
(2015) 57–64, doi:http://dx.doi.org/10.1016/j.jenvman.2014.09.030.
[57] D. Bastani, A.A. Safekordi, A. Alihosseini, V. Taghikhani, Sep. Purif. Technol. 52
(2) (2006) 295–300, doi:http://dx.doi.org/10.1016/j.seppur.2006.05.004.
[58] X. Yuan, T.C.M. Chung, Energy Fuels 26 (8) (2012) 4896–4902, doi:http://dx.
doi.org/10.1021/ef300388h.
[59] P. Thanikaivelan, N.T. Narayanan, B.K. Pradhan, P.M. Ajayan, Sci. Rep. 2 (2012)
230, doi:http://dx.doi.org/10.1038/srep00230.
[60] M. Likon, M. Remškar, V. Ducman, F. Švegl, J. Environ. Manag. 114 (2013) 158–
167, doi:http://dx.doi.org/10.1016/j.jenvman.2012.03.047.
[61] K. Zhu, Y.Y. Shang, P.Z. Sun, Z. Li, X.M. Li, J.Q. Wei, K.L. Wang, D.H. Wu, A.Y. Cao,
H.W. Zhu, Front. Mater. Sci. 7 (2) (2013) 170–176, doi:http://dx.doi.org/
10.1007/s11706-013-0200-1.
[62] A.E.A.A. Said, A.G. Ludwick, H.A. Aglan, Bioresour. Technol. 100 (7) (2009)
2219–2222, doi:http://dx.doi.org/10.1016/j.biortech.2008.09.060.
[63] É. Pelletier, R. Siron, Environ. Toxicol. Chem. 18 (5) (1999) 813–818, doi:http://
dx.doi.org/10.1002/etc.5620180502.
[64] S.T. Nguyen, J. Feng, N.T. Le, A.T.T. Le, N. Hoang, V.B.C. Tan, H.M. Duong, J. Ind.
Eng. Chem. Res. 1 (52) (2013) 18386–18391, doi:http://dx.doi.org/10.1021/
ie4032567.
[65] M. Inagaki, A. Kawahara, H. Konno, Carbon N. Y. 40 (1) (2002) 105–111, doi:
http://dx.doi.org/10.1016/S0008-6223(01)00083-5.
[66] T. Viraraghavan, G.N. Mathavan, Oil Chem. Pollut. 4 (4) (1988) 261–280, doi:
http://dx.doi.org/10.1016/S0269-8579(88)80002-9.
[67] S.M. Sidik, A.A. Jalil, S. Triwahyono, S.H. Adam, M.A.H. Satar, B.H. Hameed,
Chem. Eng. J. 203 (2012) 9–18, doi:http://dx.doi.org/10.1016/j.
cej.2012.06.132.
[68] X. Gui, H. Li, K. Wang, J. Wei, Y. Jia, Z. Li, L. Fan, A. Cao, H. Zhu, D. Wu, Acta Mater.
59 (12) (2011) 4798–4804, doi:http://dx.doi.org/10.1016/j.acta-
mat.2011.04.022.
[69] O. Karatum, S.A. Steiner, J.S. Griffin, W. Shi, D.L. Plata, ACS Appl. Mater.
Interfaces 8 (1) (2016) 215–224, doi:http://dx.doi.org/10.1021/acsa-
mi.5b08439.
[70] D. Angelova, I. Uzunov, S. Uzunova, A. Gigova, L. Minchev, Chem. Eng. J. 172 (1)
(2011) 306–311, doi:http://dx.doi.org/10.1016/j.cej.2011.05.114.
[71] S.S. Banerjee, M.V. Joshi, R.V. Jayaram, Chemosphere 64 (6) (2006) 1026–1031,
doi:http://dx.doi.org/10.1016/j.chemosphere.2006.01.065.
[72] Z.-Y. Wu, C. Li, H.-W. Liang, Y.-N. Zhang, X. Wang, J.-F. Chen, S.-H. Yu, Sci. Rep. 4
(1) (2015) 4079, doi:http://dx.doi.org/10.1038/srep04079.
[73] M.O. Adebajo, R.L. Frost, J.T. Kloprogge, O. Carmody, S. Kokot, J. Porous Mater. 10
(2003) 159–170.
[74] M. Hussein, A.A. Amer, I.I. Sawsan, J. Anal. Appl. Pyrol. 82 (2) (2008) 205–211,
doi:http://dx.doi.org/10.1016/j.jaap.2008.03.010.
[75] J. Wang, Y. Zheng, A. Wang, Chem. Eng. J. 213 (2012) 1–7, doi:http://dx.doi.org/
10.1016/j.cej.2012.09.116.
[76] H. Zhu, S. Qiu, W. Jiang, D. Wu, C. Zhang, Environ. Sci. Technol. 45 (10) (2011)
4527–4531, doi:http://dx.doi.org/10.1021/es2002343.
[77] H. Bi, X. Xie, K. Yin, Y. Zhou, S. Wan, L. He, F. Xu, F. Banhart, L. Sun, R.S. Ruoff, Adv.
Funct. Mater. 22 (21) (2012) 4421–4425, doi:http://dx.doi.org/10.1002/
adfm.201200888.
[78] X.F. Sun, R. Sun, J.X. Sun, J. Agric. Food Chem. 50 (22) (2002) 6428–6433, doi:
http://dx.doi.org/10.1021/jf020392o.
[79] H.M. Choi, R.M. Cloud, Environ. Sci. Technol 26 (4) (1992) 772–776.
[80] T. Arbatan, X. Fang, W. Shen, Chem. Eng. J. 166 (2) (2011) 787–791, doi:http://
dx.doi.org/10.1016/j.cej.2010.11.015.
[81] D. Ceylan, S. Dogu, B. Karacik, S.D. Yakan, O.S. Okay, O. Okay, Environ. Sci.
Technol. 43 (10) (2009) 3846–3852, doi:http://dx.doi.org/10.1021/es900166v.
[82] H. Bi, Z. Yin, X. Cao, X. Xie, C. Tan, X. Huang, B. Chen, F. Chen, Q. Yang, X. Bu, X.
Lu, L. Sun, H. Zhang, Adv. Mater. 25 (41) (2013) 5916–5921, doi:http://dx.doi.
org/10.1002/adma.201302435.
[83] J. Ge, H.Y. Zhao, H.W. Zhu, J. Huang, L.A. Shi, S.H. Yu, Adv. Mater. 28 (47) (2016)
10459–10490, doi:http://dx.doi.org/10.1002/adma.201601812.
[84] A. Bayat, S.F. Aghamiri, A. Moheb, G.R. Vakili-Nezhaad, Chem. Eng. Technol. 28
(12) (2005) 1525–1528, doi:http://dx.doi.org/10.1002/ceat.200407083.
[85] V.K. Gupta, A. Nayak, Chem. Eng. J. 180 (2012) 81–90, doi:http://dx.doi.org/
10.1016/j.cej.2011.11.006.
[86] T.T. Lim, X. Huang, Chemosphere 66 (5) (2007) 955–963, doi:http://dx.doi.org/
10.1016/j.chemosphere.2006.05.062.
[87] S. Suni, A.L. Kosunen, M. Hautala, A. Pasila, M. Romantschuk, Mar. Pollut. Bull.
49 (11–12) (2004) 916–921, doi:http://dx.doi.org/10.1016/j.marpol-
bul.2004.06.015.
[88] M.H. Zhou, W. Cho, J. Appl. Polym. Sci. 89 (2003) 1818–1824.
[89] K.K. Pandey, J. Appl. Polym. Sci. 71 (May) (1999) 1969–1975 10.1002/(sici)1097-
4628(19990321)71:12<1969::aid-app6>3.3.co;2-4..
[90] J.V. Ibarra, E. Muñoz, R. Moliner, Org. Geochem. 24 (6–7) (1996) 725–735, doi:
http://dx.doi.org/10.1016/0146-6380(96)00063-0.
[91] M.A. Abdullah, A.U. Rahmah, Z. Man, J. Hazard. Mater. 177 (1–3) (2010) 683–
691, doi:http://dx.doi.org/10.1016/j.jhazmat.2009.12.085.
[92] R.S. Rengasamy, D. Das, C. Praba Karan, J. Hazard. Mater. 186 (1) (2011) 526–
532, doi:http://dx.doi.org/10.1016/j.jhazmat.2010.11.031.
[93] T.T. Lim, X. Huang, Chemosphere 66 (2007) 955–963.
[94] A. Gammoun, S. Tahiri, A. Albizane, M. Azzi, J. Moros, S. Garrigues, M. de la
Guardia, J. Hazard. Mater. 145 (1–2) (2007) 148–153, doi:http://dx.doi.org/
10.1016/j.jhazmat.2006.11.005.